Basic monoazo and disazo dyestuffs containing a hydrazinium group



3,337,523 Patented Aug. 22, 1967 The present invention is a continuation-in-part application to our copending applications Ser. No. 188,837, filed on Apr. 19, 1962, and now US. Patent 3,252,967; Ser. No. 188,889, filed on Apr. 19, 1962, and now US. Patent 3,252,965; Ser. No. 250, 787, filed on Jan. 11, 1963, now abandoned; Ser. No. 250,788, filed on Jan. 11, 1963, now

abandoned; Ser. No. 250,789, filed on Jan. 11, 1963, now

abandoned; our continuation-impart application, Ser. No. 300,068, filed on Aug. 5, 1963, now abandoned; our continuation-in-part application, Ser. No. 306,306, filed on Sept. 3, 1963; our continuation-impart application Ser. No. 306,321, filed on Sept. 3, 1963, and now abandoned; our continuation-impart application, Ser. No. 344,557, filed on Feb. 13, 1964, and now abandoned, and relates to basic dyestuffs and process for the production.

This invention relates to basic dyestufis of the formula R1 Ru )1 wherein A is a member selected from the group consisting of a radical of a monoazo and a disazo dyestutf, said dyestuffs being free from carboxylic acid and sulfonic acid groups.

y is a bridge member selected from the group consisting of NHs o,o2H,- and Ns O2CzH,

wherein p and q each stands for a positive integer of up to 6 and alkyl being lower alkyl in each occurrence thereof, R and R each is a member selected from the group consisting of hydrogen and methyl. n is a positive integer of up to 2, m is a positive integer of up to 2, and when n is 2, m is 2, and X is an anion.

These new dyes of Formula I can conveniently be prepared by replacing, or converting, n substituents Z in a compound of the formula ty )n by, or into, n groups of the formula Ha R1 11 0 Ra (III) wherein B represents A or the radical of a compound capable of the formation of a monoazo or a disazo dye A, and Z a substituent which can be replaced by, or converted into a group of Formula III; upon which the reaction product is converted by a coupling or a condensation reaction into a dye in cases where B represents the radical of a compound capable of the formation of a monoazo or a disazo dye.

A preferred mode of operation of the present process for the production of the new basic monoazo or disazo dyes comprises reacting 1 mol of a compound of the formula ty- )n wherein E represents the acid radical of an ester, with n mols of a compound of the formula and converting the reaction product into a monoazo or disazo dye, when B stands for the radical of a compound which permits the formation of a dye.

It is also possible to quaternate a compound of the formula V l E R1 (V1) with an agent yielding methyl groups, and to convert the reaction product into a monoazo or a disazo dye when B represents the radical of a compound which permits formation of a dye.

The new basic dyes of Formula I can be arrived at by alkylating a compound of the formula with an agent yielding methyl groupsand converting the reaction product into a monoazo or disazo dye when E represents the radical of a compound permitting the formation of a dye, or by reacting 1 mol of an amine of the formula B--yN Rt (VIII) wherein R represents hydrogen or the methyl group and R hydrogen or the methyl group, with n mols of a halogen amine, quaternating the reaction product with an agent yielding methyl groups if necessary, and converting it into a monoazo or a disazo dye when E represents the radical of a compound which permits formation of a dye. Here, quaternation and conversion into a dye can be carried out in either order.

Monoazo or disazo dye radicals containing metal atoms bound by coordination links can also be used. The ortho, ortho'-dihydroxy or ortho, ortho-hydroxyamino compounds, together with the ions of heavy metal such as Fe, Cu, Ni, Cr, C0, Mn are suitable for the formation of 1:1 and 1:2 metal-complex dyes.

The components B which are suitable for the formation of the monoazo or disazo dye radical A are preferably those which can be converted into the above-mentioned azo dye radicals by reaction with a diazonium salt or a coupling compound.

The azo coupling reaction is carried out in the known way, preferably in a weakly alkaline to acid medium which may be buffered if necessary.

Other suitable components B are compounds which contain a functional group or a group convertible into a functional group. These compounds are reacted with the components used for the formation of the monazo or disazo dye radical A to give the final dye of Formula I e.g. by a condensation reaction. Methylating agents which are suitable for converting compounds of the Formulae -VI, VII and, where necessary, VIII into the dye salts conforming to the present process are, e.g. the esters of strong mineral acids and organic sulfonic acids such as methyl chloride, methyl bromide and methyl iodide or dimethyl sulfate, methyl esters of low molecular alkansulfonic acids or of benzenesulfonic acid. The alkylation or quaternation is effected preferably in an inert solvent or, where suitable, in an aqueous suspension, or without solvent in an excess of the alkylating agent and at elevated temperature and in a medium which may be buffered if necessary.

The anion or anions X may be organic or inorganic ions, e.g. the ions of methyl-sulfate, sulfate, disulfate, perchlorate, chloride, bromide, iodide, phosphorus-molybdate, phosphorus-tu-ngsten-molybdate, benzene-sulfonate, oxalate, maleinate, acetate, propionate, methansulfonate, chloroacetate or 4-chlorobenzene-sulfonate.

Examples of suitable acid radicals E are those of sulfuric acid (E=SO I-I), a sulfonic acid (E=SO R where R is a substituted or unsubstituted hydrocarbon radical) and hydrogen sulfide (E=SH), but preferably the radicals of the halogen hydracids (E=Cl, Br etc.) are employed.

The reaction of a compound of Formula IV with a hydrazine of the Formula V is effected preferably in an organic solvent and at temperatures of 50 C. to +250 C. The reaction can also be carried out in aqueous medium, if necessary with the addition of an organic solvent, or without solvent at the above-stated temperatures.

The reaction of an amine of Formula *VIII with a haloge-namine is carried out preferably in an organic solvent and at tempertures of -50 C. to +80 C. The reaction can also be effected in aqueous medium if necessary with the addition of an organic solvent, at the above-stated temperatures. The halogenamine can be employed either in gaseous form or in solution in an organic solvent, in water, or in a solvent-water mixture.

The dyes formed are separated by one of the basic operations such as filtration, evaporation and filtration, precipitation from a suitable medium and filtration.

The new dyes are excellent for dyeing, padding and printing materials of polymers containing more than 80% acrylonitrile, e.g. polyacrylonitrile, e.g. Orlon (registered trademark), and copolyrners containing 8095% acrylonitrile and -5 vinyl-acetate, methyl acrylate or methyl methacrylate.

These products are marketed under the following names, most of which are registered trademarks: Acril-an (the copolymer of 85% acylonitrile and 15% vinyl acetate or vinyl pyridine), Orlon, Dralon, Courtelle, Crylor, Dynel, etc.

The dyeings on these materials obtained with the dyes of the process possess good fastness to light, washing, perspiration, sublimation, pleating, decatizing, pressing, water, sea water, bleaching, dry cleaning, cross dyeing and solvents. Some of the dyes are very good soluble in water.

The dyes of the present process are dyed to best advantage from aqueous medium, and it is preferable for the medium to be neutral or acid and of boiling temperature.

The commercially available retarding agents can be used in dyeing without adverse effect, though the new dyes produce perfectly level dyeings on the above-named polymers and copolymers without the addition of these agents. The dyes can be applied in closed equipment and under pressure, as they are highly stable in water to prolonged boilin-g. They also give very good dyeings on blend fabrics containing a polyacrylonitrile fiber or acrylonitrile copolymer fiber as one of the components. A selected number of the new dyes are suitable for dyeing polyacrylonitrile in the mass in shades fast to light and Wet fastness treatments. The dyes of the present process which possess good solubility in organic solvents are suitable for the coloration of oils, paint and lacquer media, and plastics, and for the dyeing of fiber-forming materials in the spinning solution. They have many other uses, for example the dyeing of tannin-treated cotton, wool, silk, regenerated cellulose, synthetic polyamide fibers, and paper. At all stages of manufactures it has been found that mixtures of two or more dyes of Formula I can be used with good success.

The new dyes are well suited for combination, so that dye salts of the same or different dye classes can be used for producing widely different shades.

The azo dyes obtained by the present process may belong, for example, to the ibenzene-azo-benzene, benzeneazo-naphthalene, benzene-azo-pyrazolone, benzene-azoacylacetic acid arylamide, benzene-azo-phenyl, benzeneazo-diphenyl, benzene-azo-benzene-azo-pehnol, thiazoleazo-benzene, thia-diazol-azo-pyrazolone, pyridine-azo-indole, benzene-azo-tetrahydroquinoline, benzthiazol-azotetrahydroquinoline, thiazol-azo-tetrahydroquinoline, benzene-azo-indole, benzene-azo-quinoline, benzene-azo-pyrazolidinedione, benzene-azo-indanedione, benzene-aZo-pyrrole, benzene-azo-benzo-tetrahydroquinoline or quinolineazo-benzene series etc. They can be produced by the known methods, either by coupling diazotized amines with azo components, or by oxidation coupling. The hydrazinium group can be linked to the diazoand/or the azo component, in certain cases alongside other cationic groups, e.-g. ammonium or cycloammonium groups.

Diazo compounds of the benzene, naphthalene and heterocyclic series are suitable for the production of the azo dyes of the present process. The substituents in these compounds are preferably those which are employed in the known disperse (acetate) and polyester dyes. Particularly suitable are chlorine, bromine, fluorine, nitrile, nitro, alkyl, trihalogenalkyl, alkyl-sulfonyl, sulfonamide, monoalkyl and dialkyl-sulfonamide, carbalkoxy, carboxylic acid amide, hydroxyl, alkoxy and carbalkoxy groups.

Suitable coupling components are the derivatives of the benzene, naphthalene and heterocyclic series and components having an active methylene group. Particularly suitable are the substituted aminobenzene derivatives which may be further substituted by alkyl groups and the derivatives substituted in the aromatic nucleus by e.g. substituted or unsubstituted alkyl, alkoxy, halogen, cyan, trifluoromethyl, alkanoylamino, alkyl-sulfonylamino etc. The term alkyl radical refers not only to radicals such as methyl, ethyl, propyl and butyl, but also to their substitution products (c.f. E. de Barry, Anthracene and Anthraquinone, London, 1921, p. 207), The substituents or substitution products which may be mentioned as examples are halogen, hydroxyl, as e.g. in the chloropropyl, hydroxyethyl and dihydroxypropyl radicals, ethers and esters, e.g. methoxyethyl and acetoxyalkyl radicals, the esters of carboxylic and sulfonic acids, e.g. in the carbalkoxyalkyl radical and the nitrile group, as e.g. in the cyanethyl radical.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 29.8 parts of the chloride of 1-amino-2-chloro-4-N- methyl N [a-N,N'-dimethylhydrazinio-acetyl]-aminobenzene are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at 0 with parts of normal sodium nitrite solution. The clear diazo solution is added dropwise in 30 minutes to an ice-cold solution consisting of 13.2 parts of l-hydroxy-4-methylbenzene, 200 parts of water, 40 parts of 25% aqueous ammonia solution and 10 parts of a mixture of pyridine bases. Stirring is continued at 0 until the coupling reaction is completed. The new yellow dyestulf formed is precipitated from the reaction mass by neutralization with 10% hydrochloric acid and sodium chloride, and is then filtered off, dried and ground. If necessary the dyestuff can be purified by recrystallization, e.g. from ethyl alcohol. It is a yellow brown powder which dissolves in water with a yellow coloration and is suitable for dyeing olyacrylonitrile fibers in yellow shades of very good light and wet fastness.

EXAMPLE 2 33.8 parts of the chloride of 1-amino-2-methylsulfonyl- 4-N-methyl N [a-N',N-dimethylhydrazinio-acetyl]- amino-benzene are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at with 100 parts of normal sodium nitrite solution. The clear diazo solution is added dropwise in 30 minutes to an ice-cold solution consisting of 14 parts of l-hydroxy-2,4-dimethylbenzene, 200 parts of water, 40 parts of 25% aqueous ammonia solution and 10 parts of a mixture of pyridine bases. Stirring is continued at 0 until the coupling reaction is completed. The new yellow dyestufi formed is precipitated from the reaction mass by neutralization with 10% hydrochloric acid and sodium chloride, and is then filtered ofi, dried and ground. If necessary the dyestuif can be purified by recrystallization, e.g. from ethyl alcohol. It is a yellow-brown powder which dissolves in water with a yellow coloration and is suitable for dyeing olyacrylonitrile fibers in yellow shades of very good light and wet fastness.

EXAMPLE 3 16 parts of chloroacetyl chloride are added in 20 minutes at 20 to a solution of 23.5 parts of 4-methyl-aminobenzene-aza-para-cresol in 200 parts of chloroform. After addition of 8.5 parts of sodium bicarbonate and boiling for several hours with reflux the acylation reaction is completed. After filtration the chloroform is distilled off and the residue is recrystallized from ethyl alcohol. 15 parts of the chloroacetyl derivative in a solution of 4 parts of N,N-dimethyl hydrazine and 150 parts of benzene is boiled for several hours with reflux condensation. On cooling the precipitated basic dyestuff is filtered off, dried and if necessary recrystallized. The new dyestuff dissolves in water with a yellow coloration and can be used for dyeing polyacrylonitrile fibers and containing polyacrylonitn'le fibers in mixtures in yellowshades of very good light and wet fastness.

EXAMPLE 4 27.3 parts of the chloride of 4-amino-benzer1e sulfonic acid N-methyl N fi[N,N'-dimethyl-hydrazinio]-ethylamide are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at 0 with 100 parts of normal sodium nitrile solution. The clear diazo solution is run in 15 minutes with good stirring into an ice-cold solution of 45 parts of crystallized sodium acetate in 250 parts of water, in which 21.9 parts of l-(3'-chlorophenyl)-3-methyl-5-pyrazolone is suspended in an extremely fine state. Stirring is continued at 0 and in the course of 2 hours the pH value of the dyestuff suspension is increased to 6.0 by the addition of a sufficient amount of sodium carbonate. On completion of coupling the reaction mass is heated to 35 and the whole of the precipitated dyestulf is collected on a filter. On drying and grinding there is obtained a yellow powder which dissolves in water to give yellow solutions and is suitable for dyeing olyacrylonitrile fibers in very fast yellow shades.

EXAMPLE 5 The 21.9 parts of 1-(3-chlorophenyl)-3-methyl-5-pyrazolone used in the preceding Example 4 are replaced by 18.3 parts of 1-phenyl-3-methyl-5-pyrazolone and the procedure described in that example is performed. The product is a similar dyestuif which is also suitable for dyeing olyacrylonitrile fibers in very fast yellow shades.

EXAMPLE 6 27.3 parts of the chloride of 4-amino-benzene sulfonic acid N-methyl N B[N',N'-dimethylhydr-azinio]-ethylamide are dissolved in a mixture of 17 0 parts of water and 35 parts of 30% hydrochloric acid and diazo-tized at 0 with 100 .parts of normal sodium nitrite solution. The diazo solution, which contains no excess nitrous acid, is neutralized by dropwise addition of 5% aqueous ammonia solution to the pH value of 7.5. At the same temperature a solution of 30 parts of 2,5-dimethoxy-4- chloroacetoacetic anilide in 200 parts of ethyl alcohol is dropped in at an even rate in the course of 30 minutes with good stirring. Stirring is continued at 0 until the coupling reaction is completed, after which the dyestuff is isolated in the usual way. The basic dyestuff is dried and ground to a yellow powder which dissolves in water with a yellow coloration and is suitable for dyeing polyacrylonitrile fibers in very fast bright shades.

EXAMPLE 7 The 27.3 parts of the chloride of 4-amino-benzene sulfonic acid N-methyl-N-[i[N',N'-dimethyl-hydrazinio]- ethylamide used in Example 4 are replaced by 27.3 parts of the chloride of 4-amino-benzene sulfonic acid N-y- [N,N-dimethylhydrazinio]-propyl amide. The operating procedure is again as described in Example 4 and a similar dyestuif is obtained which dyes olyacrylonitrile fibers in fast yellow shades.

EXAMPLE 8 The 27.3 parts of the chloride of 4-amino-benzene sulfonic acid N-methyl-N-fl[N,N-dimethylhydrazinio]- ethylamide in Example 4 are replaced by 23.7 parts of the chloride of 4-amino-benzoic acid N-methyl-N-B[N',N'- dimethylhydrazinio1-ethyl amide. The operating procedure is again as described in Example 4 and a similar dyestuff is obtained which dyes polyacrylonitrile fibers in fast yellow shades.

Dyeing-Example A 20 parts of the dye obtained according to Example 1 are intimately mixed with parts of dextrin in a ball mill for 48 hours.

1 part of this preparation is pasted with 1 part of acetic acid 40%, 400 parts of distilled water at 60 are poured over the paste with constant agitation and the whole boiled for a short time. The solution is diluted with 7600 parts of distilled water, and 2 parts of glacial acetic acid are added. parts of Orlon (registered trademark) are entered in this bath at 60. The material was pretreated for 1015 minutes at 60 in a bath of 8000 parts of water and 2 parts of glacial acetic acid. The dyebath is brought to 100 in 30 minutes, boiled for 1 hour and the material rinsed. A level yellow dyeing of excellent light fastness and very good wet fastness is obtained.

Pad dyeing-Example B A padding liquor is prepared with:

Grams per liter Dye (corresponding to the dyeing preparation produced in the previous dyeing example) 50 Sodium alginate 3 Acetic acid conc. 5 Cationic softener e.g. a condensation product of 1 mol stearic acid and 1 mol triethanolamine 20 Textile printing.Example C A printing paste is made up with:

Parts Dye (corresponding to the dyeing preparation produced in the previous dyeing example) 75 Acetic acid conc. 10 Sodium alginate thickening 450 K the grouping: A cationic softener, e.g. a condensation product of Mom), 6B 2 Gliulllolgrl, S33E10 acid and 1 mol trrethanolamme 2g N(CH3)a Xe Water 415 5 The symbols K K K and the anion X in the individually presented dyes are chosen from the series displayed 1000 above or in the specification respectively. These groupings u or anions can be exchanged in any of these dyes for Polyflcrylonltflle fiber mfjltenal 15 Printed accofdlllg to another grouping or another anion in the series. Thus, the the usual hand-block printing process and subsequently b l K K may appeali place f K I may there? air-dried, Steamed for 20-30 mlflutes a Star sfeamer fore be noted as fundamental that in these dyes the symbol h satllmwd Steam: i p aggln and K with a given number may in each instance be exchanged dried P 3 fab1' 1CS a Yellow P Wlth y for any other symbol K having a number difierent from it. good fastness properties obtaln d- Further valuable basic dyestuffs, which can be produced In the followlllg Tables 3 and flthfi Symbols 1 2 15 by the procedures given in the above Examples 1 to 8 are and K represent the following groupmgs: de ribed i the f llowing Table 1.

They correspond to the formula K the grouping:

F 1 R11 N= R Anion X -N(CH3)2 X R12 R13 R14 15 K2 the grouping; wherein the symbols R -R have the meanings assigned NH CH G9 them in the said table.

G The anion X may be anyone of those named in the X specification.

TABLE 1 Ex R9 R10 11 R12 R13 R14 (EH: 9 0 CzHs H 0N H H N-C O-GH -K B 10 Cl H N02 H H N-CO-CHzK;

r 11 NCO-CH:K1 H NO: H CN CH3 CzHs 12 NC OCHz-K1 H NO: H H H 13 SOz-N H NO: H H H C2H4K1 CH3 14 SOz-N H N02 H H Cl CzH -K 15 CN H K1C3HuNH-sOz- H H H 16 NO; H K1CaHuNHSOz H H H 17 CHs-SOz- H K C3HsNHsO2- H H H 18 CN H KrCzHa-NH-SO2 H H H 19 0173 H K1C3Ha-NH-SO:- H H H H K1 CzHo-NH-S O2 H H H H K1C3H5NHS O 2- H H H H K! C3HoNH-S Orr- H H H H K C Ha-NH-S O H H H H KrCaHq-NH-SOT- H H H H Ki C aHa-NH-S O n H H H H K10 aHa-NHS O 2 H H H H K1CaHeNH-SO2 H H H CzH5 28 CON H NO: H Cl CH;

G2 4 a /CH3 29 (Jo-N H No: H H H CzH4-K1 TABLE '1Continued Ex. R9 R10 R11 12 R13 14 CH 30 N H N0 H 01 SOzC2H4-K1 OzHs 31 N H N0 H 01 SOz-C2H4K1 32 NHS02C2H4K1 H NO; H NO:

33 C1 H NO: H H

CH 34 H H SOrI TCzH4K1 H H 35 C1 H No; H H

OH; S O zI IC gH4K1 H N O 2 H H H H R1C2H4N-O 0- H OH Ex. R15 R15 R11 R15 Shade of the dyeing on e polyacrylonitrile Anion X 9 H N(C3H )a H H Orange O1 10 H 02115 7 H I H Bordeaux"; 01

11 H M02115): H H Violet Br C2H CN 12 H N H H H Scarlet OH SO4 C2H4CN 13 C1 N H H Red C1 CHa 14 H N(CH3)2 H H Red C1 CzHaCN 15 H N H H Red. G1

CgHE 02H40N 16 H N H H Ruby O1 EZHjCN 17 H N H H Red OH SO OzH CN 1s H N H CH3 Ruby 01 CzHs CzH4CN 19 n H N H CH do c1 Cz s C2H4OH 20 H N H CH3 Red-orange Br ogm C4Hu 21 H N H CH3 do O1 CgH5 22 H N(C2H4OH)2 H CH3 d0 C1 23 H N(C2H4OOCCH3)2 H C 3 d0 OH3S04 CaH4-OH 24 H N H CH3 do cmso;

CgH5 1 1 TABLE 1-Continued Ex. R15 Rm R11 R19 Shade of the dyeing on 9 polyacrylonitrile Anion X C2H4OH 25 H N H H Red-orange H804 CgHs CaH4-CN Z6 H N H H d CH3S04 C2 4CN 27 H N H H \CZH5 N(C2H4OH)1 H H N(C:H5)2 H H Orange Cl N(C:H5)2 H H Bordeaux Cl N(C2H5)1 H H Cl N(CHa)z H H Ruby Cl (CH2)4K1 33 H N H H Red CHaSO CzH5 34 OH; H H 011 Yellow Cl C2H4-OC2H4-K1 H N H H Red 01 CzHgCN 36 H N H H Red C1 CzH5 37 H H CH3 H Yellow 01 Further valuable basic dyestufi', which can be produced by the procedures given in the above Examples 1 to 8 are described in the following Table 2.

They correspond to the formula R20 19 Iiao RN 6) R11 N=N R 5 Q 8 v Anion X 25 R26 wherein the symbols R -R have the meanings assigned them in said table.

The anion X may be anyone of those named in the specification.

TABLE 2 Ex. Rm 20 Rn R2: R2: 24 R1:

38 H SO2NH(CH2)3K: H H H H H 39 CON H NO: H H H H C:H4K1

CH 40 SOgN H NO: H H H H C2H4-Kl CH; 41 SO2-1 IC2H4-K1 H N0: H H H H CH 42 SOrI ICzH4-Ki H NO: H H H H 43 SOzNC:Hr-K1 H NO: H H H H TABLE 2Continued Shade of the Ex. R R11 Rga R R dyeing on POI- Anion X yacrylonitrile 54 H H H H OH Orange -w Q;

55 H H H H OH GIG-SO:

56 H H H H OH do Br The base of the hydrazinium grouping need not necessarily be a coupling or a diazo component of the benzene 15 or naphthalene series as in the above examples, but can also be a heterocyclic coupling componud or a diazo component.

Further valuable basic dyestufl of this series, which can 20 also be produced by the procedures given 1n the above Examples 1 to 8 are described in the following table. They correspond to the formula Rea R61 35 25 Reg N=N-C -C--R74 I l 1 Anion x R10 R71 Rn N R13 0 wherein the symbols R -R' have the meanings assigned them in said table.

The ianion X may be of those named in the specification.

TABLE 3 Ex. Ru Ros Rea R10 R11 57, 0 CH3 SO2-NH-C 3H5K1 H H H H CH CHgNHC 0 CH2K1 0H3 H CH3 oHzNHcocm-Kl OH;

H CH3 CHiNH o o GHQ-K1 OH;

H CH3 oHiNH o 0 CHT"K1 CH3 H CH3 oHzNHoocHHm Cm H CH3 CHzNHC O GHQ-Kr CH3 H CH3 'CHzNHC 0 0112-111 CH;

H CH3 CHzNH C O CHz-Ki OH;

H CH3 CHZNH o 0 OH:K1 CH;

H CH3 CHrNHC O CH2K1 CH3 H CHQNHC 0 OHa-Ki OHZ H H GHiNHc: o GHQ-Kl OH; H

H CHQNHC 0 OIL-K1 CH3 H H CHrNHC O CHi-Kl CHa H H CH3 OHQNHCOCHl-Kl H H (JHiNHoooHr-Ki OCH: H

No, CH3 0H,NHcooH,-K1 OCH;

H H H H H NBC 0 0H; H H

H N HC 0 02115 H H H C O O CzHr H H Ex. B1: R1; R14 Shade of the dying on Anion Polyacrylonitrile X% 57 0H 0 CH3 Yellow 01 5s OH H CH3 -.do 01 59 0H H CQ-NH; c1

TABLE 3Oontinued Ex R1 R13 R14 Shade of the dying on Anion Polyacrylonitrile 60 OH CH3 CH3 Yellow cmso.

61 OH CzH4CN CH3 d 0113304 62 0H 02114011 CH3 .do Cl 63. on 0 CH3 a 01 C1 64 O 0 CH3 do 01 e 0H 0N0; CH3 Reddish-yellowc1 s3 OH -NH-c 0-0113 CH; do 01 NHz CH; Cl

802-011: CH3 Greenish-yellow Cl SOz-N(CH3): CHa dO C1 S02 CHa CH3 do C1 -0l 71 NH: 0 CH3 --do 01 72 OH 0 0000113 Yellow c1 01- 7s OH 0 CH3 Reddish-yellow c1 74 N112 0111-0110110 C Ha Orange 0113304 CH3 75 0H 6-0113 0113 Yellow CHQSO;

I CHzNHC O CHr-K 3 OH --C-1 (IJH2NHC O QHPK! CHzNHC O GHQ-K1 OH CH3 CH3 d0 C1 78 CHZNHC o GHQ-K1 Further valuable basic dyes, which can be produced by the procedures given in the above Examples 1 to 8 are described in the following Table 4.

They correspond to the formula l R7 N=N-R Anion X l R78 Rn wherein the symbols Rqs-Rgo have the meanings assigned them in said table.

The anion X may be anyone of those named in the specification. 1 i

6 .dwii- JwO OO HHO O D CE EH00 mM -MOOOMZJMO JMO 52 m 43 \O O MO 6 tow}-.- m GH HHQOOHHZ MO mmOOOONZ N m na O O HO is}--- NO Om WO O0 05 m mM mOOONZ MO :QOOOOWZ m m mo" om mo 26? O O o mw o O o m Hm mM mOOOmZ mO MRVOOUHHZ M m ZO JMJV Mn-V z 6 m m JHO MO m Q JWOOOHWZAWO ERVOOOUEZ M H con JNJV NZ 6 0 m HHO NO m MT NOOOHMZSMO m-OOOOmZ m H 8 5 ion}-.- O SmO HHZ O O HHO O O OJW m M NO O ONZJHO EQO O O DMZ m M mm sw mo 26? MO ZJWOVMZ OO MO O 0 0 m m -M -MOOOMZ-HO HQOAVOOMZ m m l .3 wZ mo w sm mo z h Eu m O 0 m m 6 GH ND O OMZ WO H AND O 3 ammo 6 low-ll B Q HZ OO HXU O O UNN m 6 GH HHOOONVQNO m MOO 3 H6 0 -MO% 6 SEW U NZ O O mnw o 0 0 m m 6 M nmnv O ONZJMO m END 0 1 Jo HO O os ocmaomfiom un q2n no N E? 3 2 2m R :m w 8 3 mm 29 30 Formulae of representative dyes of the foregoing exwherein amples are as follows: p and q each stands for a positive integer of up to EXAMPLE 36 6 and Flkyl being lower alkyl in each occurrence thereo F I 99 R and R each is a member selected from the group consisting of hydrogen and methyl,

C2H4CN 9 n is a positive integer of up to 2, OzN C m is a positive integer of up to 2, and when n is 2, m

H is 2, 2 5

10 and EXAMPLE 37 X is an anion. 0H, 9 2. A basic dye according to claim 1, said basic dye being of the formula H3 iI I 2Hi1 I-0C- Q 019 CH; NH2 3;

NH; CH3 SOzI q-C2H4l 1'(CHa)a 0H oiHicN e 40 036M304 r CH3 NH; CH3 CZHE in g of the formula I OzN N=N H3 019 cm e 2 (CHS)ZITICIHA III OCON=NO o1 NEH I sorNwzHrNwfim NH Q 3 A basic dye according to claim 1, said basic dye be EXAMPLE 44 4. A basic dye according to claim 1, said basic dye NHCH3 59 being of the formula OzN N=N- 7 CH3 NH, CH3 9 SO2NC2H4N(CHa)z NH CH 1 1m I 6 e S O 2-I TC2H4-N (CH3) 2 O2N@ N N H3 01 EXAMPLE 88 TH: (IE8 W 5Ab'd d 1 1 'db'd as1c ye accor ing to c aim sa1 as1c ye (CH3)1N 02H, N 023 ON N W 016 being of the formula 40 o1 NH-CH a; NH I 3 Having thus disclosed the invention what we claim is: O NC -N=N OH N C19 1. A basic dyestufi of the formula I 3 I 2 S0y-NC H N(CH r E me? 6. A basic dye according to claim 1, said basic dye AyNCH being of the formula L 1 Xme 1 111, 2113 e Ri Ri n (I) (CH3)2N C2H4NO2SON=NC [1 6 Wherem I H3C C A is a member selected from the group consisting of g a radical of a lmonoazo and a disazo dyestufi, said N I 'd d ulf c gsemg free from carboxylic am an s om References Cited y is a bridge member connected an an 1 nucleus of A UNITED STATES PATENTS and iS S1Ct6d from the group consisting of 2 357 317 9 194 Dickey 260 205 a yl a lkyl 2,955,108 10/ 1960 Omietanski 260-205 3 183 224 5/1965 Benz et a1 260-146 CH -N-COOH -0 O-NC H- e e 2 3,190,371 6/1965 Auerbach et a1 260-446 3,206,451 9/1965 Benz et a1 260153 'SOrNHCaHe-, -SO2NC2H4, 2)n 2)q alkyl CHARLES B. PARKER, Primary Examiner. 

1. A BASIC DYESTUFF OF THE FORMULA 